EP1099670B1 - Composition de verre-mère pour lentille à gradient d'indice - Google Patents

Composition de verre-mère pour lentille à gradient d'indice Download PDF

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Publication number
EP1099670B1
EP1099670B1 EP00124245A EP00124245A EP1099670B1 EP 1099670 B1 EP1099670 B1 EP 1099670B1 EP 00124245 A EP00124245 A EP 00124245A EP 00124245 A EP00124245 A EP 00124245A EP 1099670 B1 EP1099670 B1 EP 1099670B1
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EP
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Prior art keywords
mol
glass
zro
glass composition
zno
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP00124245A
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German (de)
English (en)
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EP1099670A1 (fr
Inventor
Tetsuro Yoshii
Shigeo Kittaka
Tadashi Koyama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Sheet Glass Co Ltd
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Nippon Sheet Glass Co Ltd
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Publication of EP1099670A1 publication Critical patent/EP1099670A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

Definitions

  • This invention relates to a mother glass (i.e., homogeneous glass before ion exchange) composition suited for producing graded index lenses having a refractive index gradient in its cross section. More particularly, it relates to a glass composition for graded index lenses, which is excellent in drawability and ion-exchanging properties.
  • a mother glass i.e., homogeneous glass before ion exchange
  • a graded index lens is a rod lens having a refractive index distribution in its cross section varying from the center axis toward the periphery. It has many advantages such that it has an image forming action even with flatness on both sides and can easily be processed into a microfine lens. Therefore, it has recently enjoyed wide application to an optical system for copiers, facsimiles, LED array printers, liquid crystal shutter printers, etc.
  • a graded index lens having such wide applicability is usually produced by an ion-exchange process, in which a glass body containing a first cation capable of constituting a modified oxide is immersed in a high-temperature molten salt containing a second cation capable of constituting a modified oxide to exchange the first cation in the glass body for the second cation in the molten salt thereby forming a refractive index distribution changing from the center of the glass body toward the periphery.
  • JP-B-51-21594 discloses a process for obtaining a graded index lens having a greater angular aperture, in which Li-containing glass body is subjected to ion exchange in molten sodium nitrate.
  • TiO 2 is effective for providing a large refractive index difference
  • ZrO 2 is effective for providing an improved chemical resistance.
  • the glass composition can further contain Ta 2 O 5 or Nb 2 O 5 as a component for replacing a part of TiO 2 and increasing the refractive index difference without increasing the dispersion of the lens.
  • JP 63170247 A is concerned with titled glass which has a large ion exchange speed, refractive index difference between the periphery and center of a rod and aperture and has a small chromatic aberration, by subjecting SiO 2 -Li 2 O 5 -(RO+ZrO 2 )-TiO 2 glass having a specific composition to an ion exchange treatment.
  • a high-temperature fused salt e
  • the concentration gradient of alkali metal ions changing continuously from the outside to the inside is thus formed in the glass body.
  • EP 0 953 548 A1 relates to a process of producing a glass substrate for an information recording medium by press-shaping a molten glass which gives a glass containing 0.1 to 30 mol% of TiO 2 , 1 to 45 mol% of CaO, 5 to 40 mol% of total of MgO and the above CaO, 3 to 30 mol% of total of Na 2 O and Li 2 O, 0 to 15 mol% of Al 2 O 3 and 35 to 65 mol% of SiO 2 and having properties of a liquidus temperature of 1, 360°C or lower and a viscosity of at least 10 poise in a shaping-allowable temperature range, or by preparing a preform formed of a glass which contains 0.1 to 30 mol% of TiO 2 , 1 to 45 mol% of CaO, 5 to 40 mol% of total of MgO and the above CaO, 3 to 30 mol% of total of Na 2 O and Li 2 O, 0 to 15 mol% of Al 2 O 3 and 35 to 65
  • JP 11302035 A is concerned with optical glass for mold press molding.
  • the weight ratio of Li 2 O to (TiO 2 +ZrO 2 ) is in the range of 0.95-3.5.
  • EP 0 657 391 A1 relates to glasses essentially free of lead displaying physical characteristics of lead-containing crystal glasses. They exhibit a density of at least 2.9g /cm 3 and an index of refraction of at least 1.545 and which consist essentially of the following composition expressed in terms of weight percent on the oxide basis of SiO 2 : 51-63, Li 2 O: 0-3, Na 2 O: 0-8, K 2 O: 0-12, Li 2 O+Na 2 O+K 2 O: 7-15, SrO: 0 - ⁇ 8, BaO: >13-21, ZnO: 5-15, SrO+BaO+ZnO: 27-34, Al 2 O 3 : 0-5, ZrO 2 :0-6, SiO 2 +Al 2 O 3 +ZrO 2 : 55-66, TiO 2 : 0-3, CaO: 0-5, MgO: 0-3, B 2 O 3 : 0-3, La 2 O 3 : 0-8.
  • An object of the present invention is to provide a mother glass composition for graded index lenses which has a small dispersion and suitability to large-scale production.
  • the present inventors have conducted extensive investigations and, as a result, have found that incorporation of specific amounts of specific components which are selected from oxides of the metal elements having an atomic number of 30 (Y) to 73 (Ta) and which hardly cause coloration into PbO-free SiO 2 -TiO 2 -Li 2 O-Na 2 O-based glass provides a glass composition which has a desirable refractive index, hardly undergoes devitrification, and hardly develops cracks on ion exchanging and is suitable as a mother glass composition for a graded index lens.
  • the mother glass composition for graded index lenses according to the invention comprises, as glass components,
  • the content of BaO is preferably equal to or less than that of MgO, in order to prevent devitrification. Furthermore, it is the content of ZnO is 1 to 5 mol% with the total content of ZnO, ZrO 2 , Y 2 O 3 , and La 2 O 3 being 3 to 10 mol%, in order to suppress crack development during ion exchange. Moreover, the total content of Y 2 O 3 , and La 2 O 3 , is preferably 1 to 9 mol%.
  • a mother glass composition shown in Table 1 below was formed into a rod having a diameter of 1.1 mm, and its refractive index, Abbe's number, and devitrification temperature were measured.
  • the glass rod was treated in a molten sodium nitrate bath under conditions shown in Table 1 to effect ion exchange.
  • the resulting glass rod was inspected for surface opacity and cracks.
  • the glass rod was processed into a lens, and the lens performance such as an angular aperture was evaluated according to the following methods. The results obtained are shown in Table 1.
  • the glass rod was cut to appropriate lengths, and both cut sides were polished for mirror finish to obtain a rod lens.
  • a checkered pattern was brought into contact with one side of the lens, and the length at which an image of the checkered pattern is obtained from the other side was obtained.
  • a refractive index distribution coefficient ⁇ A was calculated from the length.
  • the mother glass was broken into pieces having a diameter of about 1 mm and thoroughly washed with methanol.
  • the broken pieces were put in a platinum boat of 200 mm in length, 12 mm in breadth, and 8 mm in depth and maintained in a gradient furnace of 600 to 1025°C for 1 hour.
  • Development of devitrification was observed with the naked eye, and the degree of devitrification was graded A (imperceptible), B (slight) or C (considerable).
  • a mother glass composition shown in Table 2 below was formed into a glass rod in the same manner as in Examples 1 to 5.
  • the mother glass was evaluated in the same manner as in Examples 1 to 5.
  • the results obtained are shown in Table 2. It is seen that the angular apertures are generally slightly greater than those of Examples 1 to 5.
  • a mother glass composition shown in Table 3 below was formed into a glass rod in the same manner as in Examples 1 to 10.
  • the mother glass was evaluated in the same manner as in Examples 1 to 10.
  • the results obtained are shown in Table 3. It is seen that the glass of Examples 11 to 15 is less susceptible to devitrification, and the resulting lenses have greater angular apertures than those of Examples 1 to 10.
  • the glass rods suffered from no opacity nor cracks which tend to develop on the surface during ion exchange.
  • a mother glass composition shown in Table 4 below was formed into a glass rod in the same manner as in the foregoing Examples.
  • the glass was evaluated in the same manner as in the foregoing Examples. The results obtained are shown in Table 4. It is seen that the glass is less susceptible to devitrification, and the lends have greater angular apertures than those of Examples 1 to 10. Further, the rods suffered from no opacity nor cracks which tend to develop on the surface during ion exchange. In addition, the graded index lenses prepared from these glass rods show improvement of lens performance over those of Examples 11 to 15.
  • the glass compositions according to the present invention have an angular aperture (half angle) of 10° or more and an Abbe's number, which is indicative of dispersion, of 40 or more, proving less susceptibility to devitrification.
  • glass rods were prepared from the comparative glass compositions shown in Table 5 below. Although all the resulting glass rods have an angular aperture of 10° or more, the composition containing a lead compound has an Abbe's number of less than 40 which is unfavorable for use as a lens, and the compositions containing no lead compound and having an angular aperture of about 10° are extremely susceptible to devitrification.
  • SiO 2 is a main component forming the glass network structure. If the SiO 2 content is less than 45 mol%, the composition does not vitrify. If it exceeds 65 mol%, the proportion assigned to the other components serving to reduce the melting temperature or to improve the refractive index is so limited that practical glass cannot be obtained.
  • Li 2 O is one of the most important components for ion exchange. If the Li 2 O content is less than 8 mol%, the refractive index difference obtained by ion exchange is too small to obtain a sufficient angular aperture for practical use. If the Li 2 O content is more than 10.5 mol%, the glass is apt to undergo devitrification.
  • Na 2 O is essential for controlling the rate of ion exchange and reducing the melting temperature. If its content is less than 5 mol%, the rate of ion exchange considerably decreases, and the melting temperature markedly increases. More than 12 mol% of Na 2 O causes reduction in chemical durability.
  • TiO 2 is essential for increasing the refractive index. The effect of less than 2 mol% of TiO 2 is insubstantial. If the TiO 2 content exceeds 15 mol%, the glass tends to undergo devitrification.
  • MgO is essential for lowering the melting temperature and making the refractive index difference greater in ion exchange treatment. Less than 2 mol% is ineffective, and more than 22 mol% tends to cause devitrification.
  • BaO is, while not essential, makes the glass less susceptible to devitrification in cooperation with MgO. Addition of more than 16 mol% of BaO tends to cause devitrification.
  • ZnO, Y 2 O 3 , ZrO 2 , Nb 2 O 5 , In 2 O 3 , La 2 O 3 , and Ta 2 O 5 are effective in increasing the refractive index. They are more effective when used as a combination of two or more thereof than used alone particularly in preventing devitrification. Note that addition of more than 7 mol% of any one of them makes the glass susceptible to devitrification. Where two or more of them are used in combination, the total content should not exceed 15 mol%. Otherwise the glass tends to be devitrified.
  • the ratio of MgO and BaO With respect to the ratio of MgO and BaO, it was ascertained that a composition containing no BaO produces a large refractive index difference by ion exchange but tends to undergo devitrification. According as MgO is displaced with BaO up to a BaO/MgO molar ratio of 1, the tendency to devitrification is improved while the refractive index difference by ion exchange is slightly reduced. If the BaO to MgO molar ratio is further increased, not only is the refractive index difference made smaller but also the tendency to devitrification increases.
  • the BaO/MgO ratio can be decided taking into consideration the effects of the other components on refractive index difference and devitrification tendency. To increase the BaO content over the MgO content is no effective means for both the refractive index difference and prevention of devitrification.
  • Lead-free glass has a relatively large Abbe's number but is liable to develop cracks during ion exchange. This tendency is coped with by incorporating 1 to 5 mol% of ZnO. Taking the effect produced into consideration in view of the balance with the refractive index, etc., the total amount of ZnO, ZrO 2 , Y 2 O 3 and La 2 O 3 is within a range of from 3 to 10 mol%.
  • the glass composition provides on ion exchanging graded index lenses having further improved lens performance.
  • the glass composition of the invention can further comprise, as auxiliary components, 0 to 3 mol% of K 2 O, 0 to 5 mol% of CaO, 0 to 5 mol% of SrO, 0 to 1 mol% of SnO, 0 to 5 mol% of B 2 O 3 , 0 to 5 mol% of Al 2 O 3 , 0 to 3 mol% of Bi 2 O 3 , 0 to 3 mol% of Ce 2 O 3 , 0 to 3 mol% of WO 3 , and 0 to 0.5 mol% of As 2 O 3 . Incorporation of these auxiliary components will enable fine control on angular aperture or solubility. (mol%) Example No.
  • the present invention provides glass for graded index lenses which has reduced dispersion to secure improved lens performance and which hardly undergoes devitrification and thereby exhibits improved drawability.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Glass Compositions (AREA)

Claims (6)

  1. Composition de verre-mère comprenant les composants de verre suivants :
    45 à 65% en mol. de SiO2
    2 à 12% en mol de TiO2
    2 à 22% en mol de MgO
    0 à 16% en mol de BaO
    8 à 10,5% en mol de Li2O
    5 à 12% en mol de Na2O et
    3 à 15% en mol, au total, de ZnO, Y2O3, ZrO2, Nb2O5, In2O3, La2O3 et Ta2O5, à condition que la teneur en ZnO soit de 1 à 5% en mol, la teneur de chacun des Y2O3, ZrO2, Nb2O5, In2O3, La2O3 et Ta2O5 soit de 0 à 7% en mol et la teneur totale en ZnO, ZrO2, Y2O3 et La2O3 soit de 3 à 10% en mol, moyennant quoi la composition de verre ne contient pas d'oxyde de plomb.
  2. Composition de verre pour lentilles à gradient d'indice selon la revendication 1, dans laquelle la teneur en BaO est inférieure ou égale à celle du MgO.
  3. Composition de verre pour lentilles à gradient d'indice selon la revendication 1, dans laquelle la teneur totale en Y2O3 et La2O3 est de 1 à 9% mol.
  4. Lentille à gradient d'indice comprenant une composition de verre-mère, dans laquelle la composition de verre-mère comprend les composants de verre suivants :
    45 à 65% en mol de SiO2
    2 à 12% en mol de TiO2
    2 à 22% en mol de MgO
    0 à 16% en mol de BaO
    8 à 10,5% en mol de Li2O
    5 à 12% en mol de Na2O et
    3 à 15% en mol, au total, de ZnO, Y2O3, ZrO2, Nb2O5, In2O3, La2O3, et Ta2O5, à condition que la teneur en ZnO soit de 1 à 5% en mol, la teneur de chacun des Y2O3, ZrO2, Nb2O5, In2O3, La2O3, et Ta2O5 soit de 0 à 7% en mol et que la teneur totale en ZnO, ZrO2, Y2O3 et La2O3 soit de 3 à 10% en mol, moyennant quoi la composition de verre ne contient pas d'oxyde de plomb.
  5. Lentille à gradient d'indice selon la revendication 4, dans laquelle la teneur en BaO est inférieure ou égale à celle du Mgo.
  6. Lentille à gradient d'indice selon la revendication 4, dans laquelle la teneur totale en Y2O3 et La2O3 est de 1 à 9% en mol.
EP00124245A 1999-11-11 2000-11-10 Composition de verre-mère pour lentille à gradient d'indice Expired - Lifetime EP1099670B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP32105499 1999-11-11
JP32105499A JP2001139341A (ja) 1999-11-11 1999-11-11 屈折率分布型レンズ用母材ガラス組成物

Publications (2)

Publication Number Publication Date
EP1099670A1 EP1099670A1 (fr) 2001-05-16
EP1099670B1 true EP1099670B1 (fr) 2003-09-17

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EP00124245A Expired - Lifetime EP1099670B1 (fr) 1999-11-11 2000-11-10 Composition de verre-mère pour lentille à gradient d'indice

Country Status (6)

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US (1) US6476975B1 (fr)
EP (1) EP1099670B1 (fr)
JP (1) JP2001139341A (fr)
CN (1) CN1210220C (fr)
DE (1) DE60005274D1 (fr)
TW (1) TW496854B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2614762C1 (ru) * 2016-02-29 2017-03-29 Юлия Алексеевна Щепочкина Стекло
RU2631709C1 (ru) * 2016-10-31 2017-09-26 Юлия Алексеевна Щепочкина Стекло

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TW530166B (en) * 2001-01-05 2003-05-01 Schott Glass Tech Inc Interference filter having a glass substrate
TW200303995A (en) * 2002-02-22 2003-09-16 Nippon Sheet Glass Co Ltd Planar lens and its producing method
TW200405139A (en) 2002-09-04 2004-04-01 Nippon Sheet Glass Co Ltd Glass composition for graded-index rod lens cover, graded-index rod lens, and method for manufacturing the same
JP2004219554A (ja) * 2003-01-10 2004-08-05 Olympus Corp 光通信用レンズ系、光ファイバコリメータ、及び光アイソレータ
JP4013913B2 (ja) 2004-04-05 2007-11-28 日本板硝子株式会社 鉛フリーの屈折率分布型レンズ用母材ガラス組成物、屈折率分布型レンズ、屈折率分布型レンズの製造方法、光学製品及び光学機器
JP2006056768A (ja) 2004-07-23 2006-03-02 Nippon Sheet Glass Co Ltd 屈折率分布型ロッドレンズ用クラッドガラス組成物、およびそれを用いた屈折率分布型ロッドレンズ母ガラスロッド、ならびに屈折率分布型ロッドレンズ、およびその製造方法
CN1828338B (zh) * 2005-02-28 2010-08-25 鸿富锦精密工业（深圳）有限公司 透镜
JP5274855B2 (ja) * 2007-02-19 2013-08-28 日本板硝子株式会社 屈折率分布型レンズ用母材ガラス組成物、屈折率分布型レンズとその製造方法ならびに光学製品および光学機器
FR2926544B1 (fr) * 2008-01-18 2011-04-22 Eurokera Article vitroceramique et email adapte pour son revetement
CN112166091A (zh) * 2018-06-01 2021-01-01 日本电气硝子株式会社 强化玻璃以及强化用玻璃
JP7488260B2 (ja) 2018-11-26 2024-05-21 オウェンス コーニング インテレクチュアル キャピタル リミテッド ライアビリティ カンパニー 改善された弾性率を有する高性能ガラス繊維組成物
BR112021010112A2 (pt) 2018-11-26 2021-08-24 Owens Corning Intellectual Capital, Llc Composição de fibra de vidro de alto desempenho com módulo específico melhorado
CN114613529B (zh) * 2022-05-07 2022-08-16 西安宏星电子浆料科技股份有限公司 一种无铅厚膜电阻浆料

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JPS5121594B2 (fr) 1971-12-25 1976-07-03
JPS5941934B2 (ja) * 1980-12-05 1984-10-11 日本板硝子株式会社 光集束性レンズ用ガラス組成物
JPS63170247A (ja) * 1986-12-29 1988-07-14 Ohara Inc 屈折率分布ガラスの製造方法
EP0287345A1 (fr) * 1987-04-16 1988-10-19 Canon Kabushiki Kaisha Composition de verre et méthode de préparation d'une lentille à gradient d'indice
FR2713622B1 (fr) * 1993-12-10 1996-03-01 Corning Vitro Corp Verres ne contenant pas de plomb et présentant les caractéristiques du cristal.
US6332338B1 (en) * 1997-07-30 2001-12-25 Hoya Corporation Method of producing glass substrate for information recording medium
JPH11302035A (ja) * 1998-04-17 1999-11-02 Nippon Electric Glass Co Ltd モールドプレス成形用光学ガラス

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2614762C1 (ru) * 2016-02-29 2017-03-29 Юлия Алексеевна Щепочкина Стекло
RU2631709C1 (ru) * 2016-10-31 2017-09-26 Юлия Алексеевна Щепочкина Стекло

Also Published As

Publication number Publication date
JP2001139341A (ja) 2001-05-22
CN1210220C (zh) 2005-07-13
US6476975B1 (en) 2002-11-05
CN1295986A (zh) 2001-05-23
DE60005274D1 (de) 2003-10-23
EP1099670A1 (fr) 2001-05-16
TW496854B (en) 2002-08-01

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